Color forming compounds containing sulphonamide groups



Patented N v. 14, 1944 COLOR FORMING COLIPOUNDS CONTAINING SULPHONAMIDE GROUPS Paul W. Vittnm, Willard D. Peterson, and Henry D. Porter, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a cor- I notation of New Jersey No Drawing. Serial No.

Original application Aplll 5, 1939, 266,152, now Patent No. 2,271,238,

dated January 27, 1942. Divided and this application July 26, 1941, Serial No. 404,234.

Great Britain March 31, 1939 6 Claims.

This invention relates to photographic color forming compounds' and particularly to color forming coupler compounds containing sulphonamide groups. 7

This application is a division of our application Serial No. 266,152, filed April 5, 1939,-now Patent 2,271,238, granted January 27, 1942.

The use of color forming compounds which react with the development product of primary arcmatic amino developing agents to form color images on photographic development is well known and has been the subject of numerous prior patents. The dyes formed in this way are insoluble in water and .in the ordinary photographic developing and fixing baths although the silver images formed simultaneously with them during the photographic development may be removed from the photographic layer to leave pure dye images in the layer. The coupler compounds used in this way may be added to the developing solution or in certain cases may be incorporated in the photographic layer prior to exposure.

where Z represents a phenol or naphthol nucleus and It represents an aryl radical other than a a,

. hydroxy-substituted aryl radical.

when the coupler compounds are incorporated in the developing solution, it is desirable that they. be sumciently soluble in the developing solution so that amounts may be used which produce suillciently high dye densities in the resulting photographic image. In many cases the coupler compounds are not sumclen'tly soluble in the developat and steps mustbetakentoincreasetheir solubility.

In Schinzel application Serial No. 263,945, filed March 24, 1939, a continuation-in-part. of Serial No. 151,811, flied July 3, 1937, now Patent 2,306,- 410, granted December 29, 1942, phenolic and naphtholic coupler compounds are which contain sulphonamide groups in which the sulphur of the sulphonamide is attached to the phenol or naphtho'l. These compounds are high- 1y soluble in the developing solutions and produce dyes which are transparmt and are notcloudy oropsmieasisthecasewithmanydyesproducedinthisway. Thcsedyesare however, subject to decomposition by the action of heat and light and it is, therefore, desirable to produce dyes having the solubility and light characteristics of the dys described in the Schinsel application but which are more stable to heat and light. 7

It is, therefore, an object of the present'inven tion'to provide novel photographic coupler compounds having desirable properties with respect to heat and light stability. A further object is to provide photographic couplers which are highly soluble in developing solutions. A still further Compounds representing this general class are as follows:

Ham-niphonamino-l-nnphthol 2:4-dichloIo-6-(p-toluene sulphamino)-l-naphthol 5(l,2,3,4-tehahydronaphthslene-6-snlphonamiuo)-l-nsphthol I 2,4-dichloro-b-(4-bromodiphenyl-4-sulphonamino)-l-naphthol I OH U I o-(fl-naphtbaleneaulphonamino)-phanol S O2-N 5-(m-nitrobenzenesulphonamino)-l-naphthol l l I N I S Or-N I 6-iquinoline-5-sulphonamino)-1-naphthol The coupler compounds having the general formula:

have a phenol or naphthol nucleus attached to the nitrogen but not to the sulphur of the sulphonamide group. We have found that the heat and light stability characteristics of the resulting dyes are materially improved when the group attached to the sulphur of the sulphonamide portion of the molecule is a radical not containing a hydroxyl group.

The phenol or naphthol nucleus is a. functional or coupling group capable of reacting with the oxidation product of primary aromatic amino photographic developers to produce cyan or bluegreen dye images.

A. p-Aminodiethylaniline hydrochloridegrams Sodium sulphite (anhydrous)- do 5 Sodium carbonate (anhydrous) ....do 20 Potassium bromide --do 2 Water to cc 1000' B. 2,4-dichloro-5-benzene-sulphonamincl-naphthol "gram" 1 Isopropylalcohol cc 100 B is added to A sensitive salt as a chemical combination. In the case of a multi-layer photographic him in which color forming compounds may be incorporated in one or more of the layers, it may be necessary to take special precautions to prevent wandering of the coupler compound from-the sensitive layer in which it is incorporated. Certain of the coupler compounds'described in the present application are in themselves non-diflusing and may be incorporated in the photographic layer without the use of additional agents to prevent diffusion.

The sulphonamide group, because of its solubilizing eflect, has a very important advantage in connection with non-diii'using couplers in that it makes dispersion of the couplers very much easier. Thus it is ossible to have a coupler of high molecular weight which is completely non-diffusing and yet which is simply and easily dispersed due to the salt-forming properties of the S02-NEI- amines. These compounds are usually used in the salt form, such as the hydrochloride or the sulphate, which are more stable than the amines themselves. Suitable compounds are diethyl-pphenylenediamine hydrochloride, monomethyl-pphenylenediaminehydrochloride, phenylenediaminehydrochloride and dimethyl-pphenylenediaminesulphate. The p-aminophenols and their substitution products may also be usedwhere the amino group is unsubstituted. All of .these compounds have an unsubstituted amino group which enables the oxidation products of the developer to couple with the color forming compounds to form a dye image.

Our development process may be employed for the production of colored photographic images in layers of gelatin or other carrier, such as collodion, organic esters of cellulose, or synthetic resins. The carrier may be supported by a transparent medium such as glass, a cellulose ester' by coupling may be bleached by an oxidizing agent such as chromic acid to colorles soluble compounds. The destruction of the dye in this way does not destroy the silver image and'a silver image may be developed, bleached and developed to 'color a number of times, thus permitting the formation of natural color images in superposed layers as described, for example, in Marines and fiodowsky U. S. Patent No. 2,113,329.

The examples and compounds set forth in the present specification are illustrative only and it is to be understood that our invention is to be taken as limited only by the scope of the appended claims. Where we describe organic groups such as aryl, arylene, alkyl, and sulphonamide in the specification and claims, we intend to include the substituted, as well as unsubstituted, groups, except where certain groups are specifically excluded.

We claim:

1. A color-forming photographic developer comprising a rimary aromatic amino developing dimethyl p agent and a coupler compound having the formula where Z is a, naphthol radical and R is a benzene nucleus.

2. A color-forming photographic developer comprising a primary aromatic amino developing agent and a coupler compound having the formula where Z is a naphthol radical and R is a quinoline nucleus.

3. The method of producing a colored photographic image in a gelatino-silver halide emulsion layer which comprises exposing the layer and developing it with a primary aromatic amino developing agent in the presence oi a coupler compound containing only a single coupling function I and having the formula where Z is a naphthol radical, and R is an aryl radical devoid of hydroxyl groups sulphonic groups, and lenco dyes.

4, A photographic emulsion for forming colored images comprising a carrier containing a sensitive silver halide and a coupler compound containing only a single coupling function and having the formula R--SO2NH-Z where Z is a naphthol radical, and R is an aryl radical devoid of hydroxyl groups, sulphonic groups and leuco dyes.

5. A color-forming photographic developer comprising a primary aromatic amino developing agent and a coupler compound containing only a single coupling function and having the for-' mula:

where Z is selected from the class consisting of phenol and naphthol radicals and R is an aryl radical devoid of hydroxyl groups, isulphonic groups and leuco dyes.

6. A color-forming photographic developer comprising-a primary aromatic amino developing agent and a coupler compound having the formula:

where Z is selected from the class consisting of phenol and naphthol radicals and R is an unsubstituted naphthalene nucleus.

PAUL W. VI'I'I'UM. WILLARD D. PETERSON. HENRY'D. PORTER. 

